Herbicidal compositions including drift retardant agents and methods of making the same

ABSTRACT

Herbicidal compositions for reducing off-site movement or drift of herbicides are described. The herbicidal compositions can include an auxin herbicide, an oil or an ester of the oil, and a polymeric emulsifying agent, such as glycerol ethoxylate-polyricinoleate, glycerol ethoxylate-poly-(12-hydroxystearate), polyethylene glycol (PEG)-polyricinoleate, PEG-poly-(12-hydroxystearate), and a combination thereof. Methods of making such compositions and methods of making such polymeric emulsifying agents are also described.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of and priority to U.S. ProvisionalApplication Ser. No. 62/959,389, filed Jan. 10, 2020, the entiredisclosure of which is hereby incorporated by reference.

TECHNICAL FIELD

The disclosure relates generally to herbicidal composition concentratesincluding at least one herbicide, such as an auxin herbicide, an oil oran ester thereof, and a polymeric emulsifying agent. The disclosurefurther relates generally to methods of making such herbicidalcomposition concentrates and methods of making the polymeric emulsifyingagent.

BACKGROUND

Auxin herbicides, such as dicamba (3,6-dichloro-2-methoxybenzoic acid)and 2,4-D (2,4-dichlorophenoxyacetic acid), are commonly used to controlauxin-susceptible plant growth on both agricultural and non-agriculturallands. Off-site movement of these herbicides has become a source ofconcern and can result in restrictions on the use of these herbicides.For example, migration of these herbicides from the application site toadjacent crop plants, such as soybeans and cotton, can occur causingcontact damage to sensitive plants. Auxin herbicide off-site movementcan occur by three primary mechanisms: physical movement or drift ofsmall particles in the spray, contamination of the sprayer, andvolatility of the herbicide after application. Monsanto has addressedvolatility by adding potassium acetate, with the trade name Vaporgrip™technology, to auxin herbicide formulations.

To address drift issues, drift retardant agents (DRAs) (also known asdrift reduction agents or drift control agents) can be included inherbicidal compositions. DRAs for herbicidal sprays can work bymodifying the size distribution of particles formed by the nozzle, forexample, by partially suppressing the formation of the smallestparticles, also known as driftable fines, which settle slowest and aremost prone to drift with the wind. Definitions of the size limit of“driftable fines” vary, but particles with a diameter below 150 μm aretypically considered susceptible to drift. There are typically two typesof DRAs. The first type of DRA is polymers, which can increase theextensional viscosity of the spray mixture. These polymers, limited incommercial practice to polyacrylamides, polyethylene oxide, and guargum, can shift the spray particle size distribution to larger diameters.While such polymers can be effective in reducing driftable fines forsome nozzles, for example, the Turbo Teejet® Induction (TTI™) nozzlefrom TeeJet and the HYPRO® Ultra Lo-Drift (ULD) nozzle, they can be lesspreferred because they can result in significantly coarser spray, whichcan provide poorer coverage, compromising weed control. Furthermore,such polymers, if incorporated into an herbicidal formulation, cangenerally result in unacceptably high viscosity.

The second type of DRA is known as “oil-type” or “emulsion-type” DRAs.As the name suggests, an oil-type DRA, largely immiscible with water,can be included in a tank formulation as an emulsion or micro-emulsion.Drift retardants of this type are available commercially as additives toa spray tank under brand names, such as Border EG (Precision Labs) andInterLock® (Winfield). These oil-type or emulsion-type DRAs can beeffective at the suppression of driftable fines, work well in a widevariety of nozzles, and can have less effect on the average particlesize of the spray; thus, providing better application coverage andherbicidal efficacy. While the use of oil-type or emulsion-type DRAs asa tank additive is common and straightforward, incorporation into anauxin herbicidal formulation remains technically challenging,particularly for producing auxin herbicidal formulations with a highload of auxin herbicide. For example, auxin herbicides, such as dicambaand 2,4-D, are typically formulated as salts in concentrated aqueoussolution. Current commercial examples are Dow's Enlist Duo® and EnlistOne™ products, which incorporate a proprietary emulsion-type DRA into anaqueous solution of the choline salt of 2,4-D. Enlist Duo® also includesthe dimethylamine salt of glyphosate. There is also a published reportfrom Clamant of a proprietary DRA that can be incorporated into thediglycolamine (DGA) salt of dicamba.

However, it is well known that stabilizing an emulsion in concentratedsalt solution is very difficult because emulsifiers perform poorly athigh ionic strength. Emulsions can be stabilized by two mechanisms,ionic repulsion and steric stabilization. At high ionic strength,electrostatic repulsion between oil droplets can be screened therebypreventing ionic stabilization. Typical nonionic surfactants, which canstabilize an emulsion by steric repulsion, rely on polyethylene glycol(PEG) chains, but PEG chains can have poor solubility and less extendedstructures in media with high electrolyte content.

These considerations along with the need to achieve high auxin loadingfavor formulations with minimal oil-type DRAs. Thus, another challengein utilizing oil-type DRAs is maintaining efficacy against drift with alimited amount of an oil-type DRA, particularly compared to oil added tothe spray tank when using commercial spray adjuvants. Accordingly, auxinherbicide compositions having a DRA incorporated therein for reducingdrift of the herbicide are desirable, particularly reduced-driftcompositions that exhibit no significant reduction in herbicidaleffectiveness relative to currently available compositions.

BRIEF SUMMARY

New and useful herbicidal compositions including a drift retardant agent(DRA) and polymeric emulsifying agent and methods of making the same areset forth in the appended claims. Illustrative embodiments are alsoprovided to enable a person skilled in the art to make and use theclaimed subject matter.

In one aspect, an herbicidal composition concentrate is described. Theherbicidal composition concentrate includes at least one herbicide, anoil or an ester of the oil, and a polymeric emulsifying agent. The atleast one herbicide can be present in an amount (acid equivalent weight)of greater than or equal to about 5% by weight of the compositionconcentrate, and the at least one herbicide can include an auxinherbicide. The polymeric emulsifying agent can be selected from thegroup consisting of glycerol ethoxylate-polyricinoleate, glycerolethoxylate-poly-(12-hydroxystearate), polyethylene glycol(PEG)-polyricinoleate, PEG-poly-(12-hydroxystearate), and a combinationthereof. In some embodiments, the herbicidal composition concentratefurther includes a surfactant selected from the group consisting of aphosphate ester, an alkylpolysaccharide, an alkoxylated castor oil, anda combination thereof. In some embodiments, the herbicidal compositionconcentrate further includes at least one monocarboxylic acid or amonocarboxylate thereof.

In another aspect, a method of making an herbicidal compositionconcentrate is described. The method includes admixing at least oneherbicide with an oil or an ester of the oil and a polymeric emulsifyingagent to form the herbicidal composition concentrate. The at least oneherbicide can be admixed in an amount (acid equivalent weight) ofgreater than or equal to about 5% by weight of the compositionconcentrate, and the at least one herbicide can include an auxinherbicide. The polymeric emulsifying agent can be selected from thegroup consisting of glycerol ethoxylate-polyricinoleate, glycerolethoxylate-poly-(12-hydroxystearate), polyethylene glycol(PEG)-polyricinoleate, PEG-poly-(12-hydroxystearate), and a combinationthereof. Ins some embodiments, the oil or the ester of the oil can beadmixed with the polymeric emulsifying agent to form a first mixture andthe at least one herbicide can be admixed with the first mixture to formthe herbicidal composition concentrate. In some embodiments, the methodfurther includes admixing at least one surfactant with the at least oneherbicide, the oil or the ester of the oil, and the polymericemulsifying agent. The surfactant can be selected from the groupconsisting of a phosphate ester, an alkylpolysaccharide, an alkoxylatedcastor oil, and a combination thereof. In some embodiments, the methodfurther includes admixing at least one monocarboxylic acid or amonocarboxylate thereof with the at least one herbicide, the oil or theester of the oil, and the polymeric emulsifying agent.

In another aspect, a method of making a polymeric surfactant selectedfrom the group consisting of glycerol ethoxylate-polyricinoleate,glycerol ethoxylate-poly-(12-hydroxystearate), polyethylene glycol(PEG)-polyricinoleate, and PEG-poly-(12-hydroxystearate) is described.The method includes contacting PEG or ethoxylated glycerol in a liquidor molten state with a C₁-C₄ alkyl ricinoleate or a C₁-C₄ alkyl12-hydroxystearate in the presence of a basic catalyst to form areaction mixture at a reaction temperature sufficient to maintain thereaction mixture in a liquid state.

Further benefits of the present invention will be apparent to oneskilled in the art from reading this patent application. The embodimentsof the invention described in the following paragraphs are intended toillustrate the invention and should not be deemed to narrow the scope ofthe invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B illustrate a mass spectrum of glycerolethoxylate-4-ricinoleate characterized by mass spectrometry withmatrix-assisted laser desorption ionization (MALDI-MS).

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

The following description of example embodiments provides informationthat enables a person skilled in the art to make and use the subjectmatter set forth in the appended claims, but it may omit certain detailsalready well known in the art. The following detailed description is,therefore, to be taken as illustrative and not limiting.

The present disclosure provides herbicidal composition concentrates, forexample, including an auxin herbicide, wherein the compositions exhibitreduced drift. Specifically, the compositions include, in addition tothe auxin herbicide, an oil or an ester of the oil, and a polymericemulsifying agent. The polymeric emulsifying agent can be selected fromthe group consisting of a phosphate ester, an alkylpolysaccharide, analkoxylated castor oil, and a combination thereof. The compositions canalso include a surfactant and/or at least one monocarboxylic acid or amonocarboxylate thereof for reducing volatility of the herbicide uponapplication.

Typically, auxin herbicides, such as dicamba and 2,4-D, are formulatedas salts in concentrated aqueous solution. It is well known thatstabilizing an emulsion in a concentrated salt solution is verydifficult because emulsifiers perform poorly at high ionic strength.Additionally, inclusion of a monocarboxylic acid or a monocarboxylatethereof for reducing volatility further increases the ionic strength ofthe composition subsequently increasing the difficulty in stabilizing anemulsion of an oil type DRA and the difficulty in preventing undesirablecreaming.

However, it has surprisingly been discovered that emulsions andmicro-emulsions of oils can be stabilized in solutions with auxinherbicides, particularly high loads of auxin herbicides in salt form(e.g., monoethanolamine (MEA) salt of dicamba), with polymericemulsifying agents including two or more polyethylene glycol (PEG)chains terminated with oligomers of fatty acids. Additionally, thepolymeric emulsifying agents described herein can be incorporated intoherbicidal compositions including auxin herbicides at levels thatimprove spray particle size distributions. The compositions providedherein can advantageously protect against drift of auxins, such asdicamba and 2,4-D, when applied with many common nozzles per labeldirections. Additionally, the compositions can provide assurance ofcompliance when a DRA is required, thus enhancing product stewardship.Incorporation of the DRA into the herbicidal composition concentratealso provides convenience and cost savings for growers and applicatorscompared to purchasing and adding an herbicide and a DRA separately. Invarious aspects, the compositions described herein provide substantialsuppression of fines with nozzles, such as, but not limited to GreenleafTurboDrop® XL (TDXL), Lechler ID, Wilger DR, Teejet® AIXR, Hypro® ULDand Teejet® TTI without significantly increasing the mean particle sizeof the spray. The compositions described herein with a built-in DRAenable improved spray quality with better coverage and weed control.

A. Auxin Herbicide Component

The term “auxin herbicide” refers to an herbicide that functions as amimic of an auxin plant growth hormone, thereby affecting plant growthregulation. Examples of auxin herbicides that are suitable for use inthe herbicidal compositions of the present invention include, withoutlimitation, benzoic acid herbicides, phenoxy herbicides, pyridinecarboxylic acid herbicides, pyridine oxy herbicides, pyrimidine carboxyherbicides, quinoline carboxylic acid herbicides, and benzothiazoleherbicides.

Examples of auxin herbicides include, but are not limited to:3,6-dichloro-2-methoxybenzoic acid (dicamba); 2,4-dichlorophenoxyaceticacid (2,4-D); 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB);dichloroprop; 2-methyl-4-chlorophenoxyacetic acid (MCPA);4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB); 4-chlorophenoxyaceticacid; 2,4,5-trichlorophenoxyacetic acid (2,4,5-T); aminopyralid;clopyralid; fluroxypyr; triclopyr; mecoprop; picloram; quinclorac;aminocyclopyrachlor; benazolin; halauxifen; fluorpyrauxifen; methyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylicacid;4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylicacid; benzyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylicacid; methyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylicacid; methyl4-amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylicacid; methyl4-amino-3-chloro-5-fluoro-6-[7-fluoro-1-(methoxyacetyl)-1H-indol-6-yl]pyridine-2-carboxylicacid; methyl6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylicacid; butyl4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylicacids, including salts and esters thereof; racemic mixtures and resolvedisomers thereof; and combinations thereof.

In any embodiment, the herbicidal composition concentrate can includedicamba, or an agriculturally acceptable salt or ester thereof. Examplesof suitable dicamba salts include, but are not limited toN,N-bis-[aminopropyl]methylamine, monoethanolamine (MEA), dimethylamine(e.g., BANVEL®, ORACLE®, etc.), isopropylamine, triethanolamine,diglycolamine (e.g., CLARITY®, VANQUISH®, etc.), potassium, and sodiumsalts, and combinations thereof. Commercially available sources ofdicamba, and its agriculturally acceptable salts, include those productssold under the trade names BANVEL®, CLARITY®, DIABLO®, DISTINCT,ORACLE®, VANQUISH®, and VISION®.

In any embodiment, the herbicidal composition concentrate can include anagriculturally acceptable dicamba salt, wherein the salt is selectedfrom the group consisting of N,N-[aminopropyl]methylamine,monoethanolamine, dimethylamine, isopropylamine, diglycolamine, apotassium salt, and a sodium salt, and combinations thereof.

Throughout the remainder of the description of the invention, wherereference is made to dicamba, or an agriculturally acceptable salt orester thereof, one skilled in the art will understand that theprinciples of the present invention apply to auxin herbicides generally,including those described above, and that the present invention is notlimited to herbicidal compositions containing dicamba, or anagriculturally acceptable salt or ester thereof.

Additionally or alternatively, the herbicidal composition concentratecan include 2,4-D, or an agriculturally acceptable salt or esterthereof. Examples of suitable 2,4-D salts include, but are not limitedto the choline, dimethylamine, triethanolamine, and isopropylaminesalts, and combinations thereof. Examples of suitable 2,4-D estersinclude, but are not limited to methyl, ethyl, propyl, butyl (2,4-DB),and isooctyl esters, and combinations thereof. Commercially availablesources of 2,4-D, and its agriculturally acceptable salts and esters,include those products sold under the trade names BARRAGE®, FORMULA 40®,OPT-AMINE®, and WEEDAR 64®.

Additionally or alternatively, the herbicidal composition concentratecan include an agriculturally acceptable 2,4-D salt, wherein the salt isselected from the group consisting of choline, dimethylamine,triethanolamine, and isopropylamine salts, and combinations thereof.

Additionally or alternatively, the herbicidal composition concentratecan include an agriculturally acceptable 2,4-D ester, wherein the esteris selected from the group consisting of butyl (i.e., 2,4-DB) andisooctyl esters, and combinations thereof.

Additionally or alternatively, the herbicidal composition concentratecan include at least two auxin herbicides, for example, dicamba, or anagriculturally acceptable salt or ester thereof, and 2,4-D, or anagriculturally acceptable salt or ester thereof.

Additionally or alternatively, the herbicidal composition concentratecan include an agriculturally acceptable auxin herbicide salt (such as adicamba salt, a 2,4-D salt, and/or a 2,4-DB salt) that is an ionicliquid as described in published application US 2013/0109572, i.e., asalt that is a liquid at a temperature at or below about 150° C. Theentire text of US 2013/0109572 is incorporated by reference into thisapplication.

B. Oil Component

In various aspects, an oil or an ester thereof is included in theherbicidal composition concentrate. The oil or an ester thereof mayserve as a DRA.

Examples of a suitable oil include, but are not limited to a vegetableoil, an ester of a vegetable oil, a petroleum-based oil, and acombination thereof. Suitable vegetable oils include, but are notlimited to soybean oil, an ester of soybean oil, canola oil, an ester ofcanola oil, palm oil, an ester of palm oil, rapeseed oil, an ester ofrapeseed oil, sunflower seed oil, an ester of sunflower seed oil, cornoil, an ester of corn oil, peanut oil, an ester of peanut oil, sesameoil, an ester of sesame oil, olive oil, an ester of olive oil, andcombinations thereof. A suitable ester of a vegetable oil include, butare not limited to a methyl ester, for example, canola methyl ester,soybean methyl ester, and so on, and an ethyl ester, for example, canolaethyl ester, soybean ethyl ester, and so on

Suitable petroleum-based oils include, but are not limited to alkanes(e.g., C₆-C₉ alkane, n-alkanes, cyclo-alkanes, iso-alkanes, etc.),distillates, naphtha (e.g., heavy naphtha, paraffinic naphtha, petroleumnaphtha, solvent naphtha, etc.), mineral oil, aliphatic oil, aromaticoil, crude oil, olefins, olefin mixtures, and combinations thereof. Inany embodiment, the petroleum-based oil can have a suitable flash point,typically greater than 150° F., for example, ISOPAR M™ (available fromExxonMobil).

C. Polymeric Emulsifying Agent Component

1. Polymeric Emulsifying Agent Structure

It has been surprisingly found that polymeric emulsifying agentsincluding two or more polyethylene glycol (PEG) chains terminated witholigomers of fatty acids can stabilize emulsions and micro-emulsions ofoils and esters thereof as described herein in solutions with auxinherbicides, particularly high loads of auxin herbicides in salt form(e.g., monoethanolamine (MEA) salt of dicamba). Additionally, thepolymeric emulsifying agents described herein can be incorporated intoherbicidal compositions including auxin herbicides at levels whichadvantageously improve spray particle size distributions.

In any embodiment, the polymeric emulsifying agent can include two ormore oligomers of ricinoleic acid or 12-hydroxystearic acid, which canbe obtained commercially from castor oil and hydrogenated castor oil,respectively. Without being bound by theory, it is believed that thepolymeric emulsifying agents described herein can be more resistant tocollapse of the PEG chains in high-ionic strength media thanconventional surfactants because the presence of two or more hydrophobes(e.g., the ricinoleate block or 12-hydroxystearate block) embedded inthe oil droplet can stretch the ethylene oxide (EO) chains of thepolymeric emulsifying agent. The fatty acid units can be linked to eachother by esterification between the C₁₂-hydroxyl and the C₁-carboxylate.The structures of these oligomers are shown below:

wherein X¹ can be H or ricinoleate and X² can be H or12-hydroxystearate.

The oligomers can be esterified to a PEG chain or an ethoxylatedglycerol, which can provide hydrophilic properties to balance thehydrophobic contribution of the fatty acid oligomers. In any embodiment,the polymeric emulsifying agent can include a PEG chain of at least 500molecular weight esterified on both ends or the hydrophile can composemultiple PEG chains. Terminal hydroxyl groups that are not esterifiedcan be bound to an organic linker, such as glycerol or polyglycerol.Glycerol with 26 ethylene oxide units, known as “glycereth-26” iscommercially available, for example, from Lonza as Ethosperse® G-26.Cocoate esters of glycerol ethoxylate with various degrees ofethoxylation are also commercially available, such as glycerol PEG-7cocoate, CAS reg. no. 68553-03-7, available from Spectrum Chemical orKao Chemical. In particular, the polymeric emulsifying agent can includean esterified ethoxylated glycerol, for example, glycerol ethoxylateesterified to poly-12-hydroxystearic acid, CAS reg. no. 1939051-18-9.

In any embodiment, the polymeric emulsifying agent can be selected fromthe group consisting of glycerol ethoxylate-polyricinoleate, glycerolethoxylate-poly-(12-hydroxystearate), polyethylene glycol(PEG)-polyricinoleate, PEG-poly-(12-hydroxystearate), and a combinationthereof. The glycerol ethoxylate-polyricinoleate can correspond instructure to Formula A:

wherein i+j+k=10 to 50 or 20 to 35 and r+s+t=3 to 12 or 4 to 8. In anyembodiment, each of i, j, and k independently can be an integer fromzero to 50, an integer from zero to 35, an integer from zero to 20, aninteger from zero to 10, an integer from 1 to 50, an integer from 1 to35, an integer from 1 to 20, an integer from 1 to 10, an integer from 5to 50, an integer from 5 to 35, an integer from 5 to 20, or an integerfrom 5 to 10. For example, i can be 1, j can be 5, and k can be 4; or ican be zero, j can be 10, and k can be 12, and so on. In any embodiment,each of r, s, and t independently can be an integer from zero to 12, aninteger from zero to 8, an integer from zero to 4, an integer from zeroto 3, an integer from 1 to 12, an integer from 1 to 8, an integer from 1to 4, an integer from 1 to 3, an integer from 2 to 12, an integer from 2to 8, an integer from 2 to 4, or an integer from 2 to 3. For example, rcan be 1, s can be 1, and t can be 1; or r can be zero, s can be 3, andt can be 5, and so on.

The glycerol ethoxylate-poly-(12-hydroxystearate) can corresponds instructure to Formula B:

wherein i+j+k=10 to 50 or 20 to 35 and r+s+t=3 to 12 or 4 to 8. In anyembodiment, each of i, j, and k independently can be an integer fromzero to 50, an integer from zero to 35, an integer from zero to 20, aninteger from zero to 10, an integer from 1 to 50, an integer from 1 to35, an integer from 1 to 20, an integer from 1 to 10, an integer from 5to 50, an integer from 5 to 35, an integer from 5 to 20, or an integerfrom 5 to 10. For example, i can be 1, j can be 5, and k can be 4; or ican be zero, j can be 10, and k can be 12, and so on. In any embodiment,each of r, s, and t independently can be an integer from zero to 12, aninteger from zero to 8, an integer from zero to 4, an integer from zeroto 3, an integer from 1 to 12, an integer from 1 to 8, an integer from 1to 4, an integer from 1 to 3, an integer from 2 to 12, an integer from 2to 8, an integer from 2 to 4, or an integer from 2 to 3. For example, rcan be 1, s can be 1, and t can be 1; or r can be zero, s can be 3, andt can be 5, and so on.

The polyethylene glycol (PEG)-polyricinoleate can correspond instructure to Formula C:

wherein j=50 to 250 or 130 to 200 and s+r=2 to 10 or 3 to 6. In anyembodiment, each of s and r independently can be an integer from zero to10, an integer from zero to 6, an integer from zero to 3, an integerfrom zero to 2, an integer from 1 to 10, an integer from 1 to 6, aninteger from 1 to 3, or an integer from 1 to 2. For example, s can be 1and r can be 3; or s can be zero and r can be 7, and so on.

The PEG-poly-(12-hydroxystearate) can correspond in structure to FormulaD:

wherein j=50 to 250 or 130 to 200 and s+r=2 to 10 or 3 to 6. In anyembodiment, each of s and r independently can be an integer from zero to10, an integer from zero to 6, an integer from zero to 3, an integerfrom zero to 2, an integer from 1 to 10, an integer from 1 to 6, aninteger from 1 to 3, or an integer from 1 to 2. For example, s can be 1and r can be 3; or s can be zero and r can be 7, and so on.

Exemplary polymeric emulsifying agents are shown below. Polymer (1)corresponds to PEG end-functionalized with ricinoleate oligomers andPolymer (2) corresponds to glycerol ethoxylate end-functionalized with12-hydroxystearate oligomers:

2. Methods of Making the Polymeric Emulsifying Agent

In various aspects, methods of making a polymeric emulsifying agent asdescribed herein are also provided. Oligomers of ricinoleic acid or12-hydroxystearic acid esterified with glycerol and other polyols areknown in the art and are prepared by first forming the oligomer,generally using acid catalysis and a solvent, followed by acid-catalyzedesterification. The oligomerization typically requires high temperaturesand/or extended times to drive off water. For example, Takeda et. al.oligomerize 12-hydroxystearic acid in toluene catalyzed byp-toluenesulfonic acid for six hours at about 200° C. with nitrogenflow. (K. Takeda, Y. Kokeguchi, H. Sone, K. Kawai, “Oil Base andExternal Preparation Containing Same,” 2008, U.S. Pat. No. 7,993,631,see Example 1.) Similarly, Yamato et. al. first oligomerize12-hydroxystearic acid in xylol at 200° C. for 15 hours with nitrogenflow. The oligomer is then esterified with di-pentaerythritol at 210° C.(Y. Yamato, Y. Oi, M. Fujisawa, “Esterification Reaction Products andCosmetic Products,” U.S. 2008/0260663, see Production Example 1).

Similar polymerization reactions can also be conducted enzymatically,but the process can be slow, and a water absorbent is required. Forexample, Zhang et. al. polymerized ricinoleic acid over Lipase PS over 7days at 60° C. in the presence of molecular sieves. (Zhang, B.-X; Azuma,J.-I.; Takeno, S.; Suzuki, N.; Nakazawa, Y.; Uyama, H., “Improvement ofthe Rheological Properties of trans-1,4-polyisoprene from Eucommiaulmoides Oliver by Tri-branched Poly(ricinoleic acid),” Polymer Journal,2016, 48, 821-7.) Esterification of ethoxylated glycerol with fattyacids also requires a prolonged reaction time under acidic conditions.For example, the esterification reaction between glycerol with 110-150ethylene oxide (EO) units and tallow fatty acid required 16 hours at160° C. (A. T. Oliva, O. P. Obiols, J. B. Llosas, E. P. Queralt, “Estersof Fatty Acids with Ethoxylated Polyols,” 1996, U.S. Pat. No. 5,576,451,to Henkel, Production Examples 1-3.)

Advantageously, the methods of making a polymeric emulsifying agent asdescribed herein can be accomplished by performing all of theesterifications in a single reactive step using esters of the fattyacids rather than free fatty acids as the starting materials. In anyembodiment, a C₁-C₄ alkyl ester can be a starting material. SuitableC₁-C₄ alkyl esters include, but are not limited to methyl esters, suchas methyl ricinoleate and methyl 12-hydroxystearate, and ethyl esters.Methanol, an exemplary byproduct or coproduct of the esterificationreactions described herein from use of a sodium methoxide catalyst, ismore volatile than water; thus, more easily driven off, whichadvantageously allows for the method described herein to be conducted atlower temperature and with shorter reaction times. Conversion of castoroil to its methyl ester, primarily methyl ricinoleate, is known in theart. (Knothe, G.; Cermak, S. C.; Evangelista, R. L., “Methyl Esters fromVegetable Oils with Hydroxy Fatty Acids: Comparison of Lesquerella andCastor Methyl Esters,” Fuel, 2012, 96, 535-40.) Both methyl ricinoleateand methyl 12-hydroxystearate (derived from hydrogenated castor oil) arecommercially available.

Preparation of the polymeric emulsifying agent described herein caninclude contacting PEG or ethoxylated glycerol with a suitable C₁-C₄alkyl ester, for example, methyl ricinoleate or methyl12-hydroxystearate, in the presence of a basic catalyst at a suitabletemperature and for a suitable time period in a suitable reaction vesselto form a reaction mixture. A suitable temperature includes atemperature sufficient for maintaining the reaction mixture in a liquidstate. Examples of a suitable temperature include a temperature ofgreater than or equal to about 70° C., greater than or equal to about90° C., greater than or equal to about 110° C., greater than or equal toabout 130° C., greater than or equal to about 150° C., greater than orequal to about 170° C., or about 180° C.; or from about 70° C. to about180° C., about 90° C. to about 170° C. or about 110° C. to about 150° C.Examples of a suitable time period include greater than or equal toabout 60 minutes (1 hour), greater than or equal to about 120 minutes (2hours), greater than or equal to about 180 minutes (3 hours), or about240 minutes (4 hours); or from about 60 minutes to about 240 minutes,about 120 minutes to about 240 minutes, or about 120 minutes to about180 minutes. Examples of a suitable basic catalyst include, but are notlimited to metal oxide catalysts, for example, a metal alkoxide or ametal hydroxide. The metal alkoxide can be a metal C₁-C₄ alkoxide, suchas, but not limited to sodium methoxide and sodium ethoxide. The metalhydroxide can include, but is not limited to sodium hydroxide, andpotassium hydroxide. In a particular, the basic catalyst can be sodiummethoxide. In any embodiment, the basic catalyst can be present in aconcentration based on the total mass of the reaction mixture of greaterthan or equal to about 0.1%, greater than or equal to about 0.5%,greater than or equal to about 1%, greater than or equal to about 1.5%,greater than or equal to about 2%, greater than or equal to about 2.5%,or about 3%; or from about 0.1% to about 3%, about 1% to about 3% orabout 2% to about 3%. As understood by a person of ordinary skill in theart the aforementioned time and temperature parameters can vary based onhow the preparation is performed, for example, length of agitation, etc.For example, the reaction mixture may be stirred or agitated undersuitable conditions to cause volatilization of the alcohol coproduct ofthe basic catalyst (e.g., C₁-C₄ alcohol coproduct such as methanol).Such suitable conditions include but are not limited to maintaining atemperature above the boiling point of the alcohol, sweeping theheadspace of the reactor with inert gas, applying a vacuum, or acombination thereof.

A slow nitrogen stream can be used to help remove the alcohol coproduct(e.g., methanol) from the reaction mixture. In any embodiment, thereaction mixture can be a homogeneous liquid, for example, PEG and/orethoxylated glycerol each can be in a liquid state or a molten state. Insome embodiments, the C₁-C₄ alkyl ester, for example, methyl ricinoleateor methyl 12-hydroxystearate, can be added dropwise to PEG orethoxylated glycerol with stirring and the reaction can continue for atleast 20 minutes after the end of the addition. In any embodiment, nosolvent is required. The basic catalyst can be neutralized with a smallamount of acid, for example, acetic acid, at the end of the reaction,and the whole reaction mass used in the formulations with no furtherpurification.

An exemplary reaction scheme below shows the reaction of PEG with methylricinoleate. Reactions involving ethoxylated glycerol or methyl12-hydrostearate follow the same reaction pathway.

D. Surfactant

The herbicidal composition concentrates described herein can furtherinclude one or more surfactants. Examples of suitable surfactantsinclude a phosphate ester, an alkylpolysaccharide, an alkoxylated castoroil, and combinations thereof. Such surfactants are particularlysuitable due to their tolerance of high levels of salt. Furthermore, thesurfactants described herein are capable of not excessively increasingthe amount of fine droplets in an agriculture spray when used at thelevels required to stabilize an oil emulsion in herbicide formulationscomprising an auxin herbicide.

In any embodiment, the surfactant may be a phosphate ester. Examples ofsuitable phosphate esters include, but are not limited to alkoxylatedphosphate esters of fatty acids. The alkoxylation may include alkoxychain of any length. For example, polyethylene oxide or polypropyleneoxide. Examples of said esters include polyethylene glycol octylphosphate, polyethylene glycol isotridecyl phosphate, polyethyleneglycol cetearyl phosphate, polyethylene glycol decyl phosphate,polyethylene glycol oleyl phosphate, polyethylene glycol polypropyleneglycol cetyl phosphate, polyethylene glycol tridecyl phosphate, andpolyethylene glycol isotridecyl phosphate. Additionally oralternatively, the phosphate ester may be ethoxylated alkyl phosphateester, for example, having less than 10 EO units. Commercially availableethoxylated alkyl phosphate esters include Crodafos™ O3 A and Crodafos™O5 A, both available from Croda, Inc.

Additionally or alternatively, the surfactant may be analkylpolysaccharide. Examples of suitable alkylpolysaccharide include,but are not limited to compounds of Formula (1):R¹¹—O-(sug)_(u)  Formula (1)wherein R¹¹ is a straight or branched chain substituted or unsubstitutedhydrocarbyl selected from alkyl, alkenyl, alkylphenyl, alkenylphenylhaving from about 4 to about 22 carbon atoms for from about 4 to 18carbon atoms. The sug moiety is a saccharide residue, and may be an openor cyclic (i.e., pyranose) structure. The saccharide may be amonosaccharide having 5 or 6 carbon atoms, a disaccharide, anoligosaccharide or a polysaccharide. Examples of suitable saccharidemoieties, including their corresponding pyranose form, include ribose,xylose, arabinose, glucose, galactose, mannose, telose, gulose, allose,altrose, idose, lyxose, ribulose, sorbose (sorbitan), fructose, andmixtures thereof. Examples of suitable disaccharides include maltose,lactose and sucrose. Disaccharides, oligosaccharides and polysaccharidescan be a combination of two or more identical saccharides, for examplemaltose (two glucoses) or two or more different saccharides, for examplesucrose (a combination of glucose and fructose). The degree ofpolymerization, u, is an average number from 1 to about 10, from 1 toabout 8, from 1 to about 5, from 1 to about 3, and from 1 to about 2.

In various embodiments, the alkylpolysaccharide may be analkylpolyglucoside (APG) surfactant of Formula (1) wherein: R¹¹ is abranched or straight chain alkyl group preferably having from 4 to 22carbon atoms or from 8 to 18 carbon atoms, or a mixture of alkyl groupshaving an average value within the given range; sug is a glucose residue(e.g., a glucoside); and u is from 1 to about 5, and more preferablyfrom 1 to about 3. In various embodiments, the surfactant componentcomprises an APG of Formula (1) wherein R¹¹ is a branched or straightchain alkyl group having from 8 to 10 carbon atoms or a mixture of alkylgroups having an average value within the given range and u is from 1 toabout 3.

Non-limiting examples of commercially available alkylpolyglucosidesinclude, for example, APG®, AGNIQUE®, or AGRIMUL® surfactants from BASFInc., for example, Agnique PG 264, Agnique PG 8105 and Agnique 8107, andTRITON™ BG and TRITON™ CG, both available from Dow, Inc.

Additionally or alternatively, the surfactant may be an alkoxylatedcastor oil, for example an ethoxylated castor oil (e.g., having lessthan 30 EO units) or a proproxylated castor oil. Alkoxylated castor oilcan be prepared by reaction of castor oil or hydrogenated castor oilwith ethylene oxide, propylene oxide, ethylene glycol, or propyleneglycol. Examples of a suitable alkoxylated castor oil include, but arenot limited to Stepantex® CO-40 (40 EO), Toximul® 8242, Toximul® 8243,Toximul® 8244, all available from Stepan Chemical Company, and Cirrasol™G-1292 (25 EO) available from Croda Inc. Other suitable examples mayinclude Emulpon™ CO-550, CO-360, CO-200 from AkzoNobel Nouryon andSurfom R® 360 and R 540 from Oxiteno.

Additionally or alternatively, the surfactant may include variousquaternary amine compounds. Quaternary amine compounds include variousalkyl/aryl quaternary amine compounds and alkoxylated alkyl/arylquaternary amine compounds including but not limited to ethoxylatedquaternary ammonium compounds.

In some embodiments, the quaternary amine compound has a structure offormula (I):

wherein R¹ is hydrocarbyl or substituted hydrocarbyl having from 1 toabout 30 carbon atoms; each R² in each of the (R²O)_(x) and (R²O)_(y)groups is independently a linear or branched C₂-C₄ alkylene; each R³ isindependently hydrogen, or a linear or branched alkyl group having from1 to about 4 carbon atoms; R⁴ is hydrocarbyl or substituted hydrocarbylhaving from 1 to about 30 carbon atoms; x and y are independently anumber from 0 to about 10; and X⁻ is an agriculturally acceptable anion.

Particular examples of quaternary amine compounds include tetrabutylammonium salts (e.g., tetrabutyl ammonium chloride and tetrabutylammonium chloride hydroxide) and trimethyl-tetradecyl ammonium salts(e.g., trimethyl-tetradecyl ammonium chloride). Other examples includethe Tomamine series of quaternary amine compounds available from Evonik,particularly the Tomamine Q-series, which are represented by formula(II):

where R is alkyl (e.g., C₁-C₂₀ alkyl), n is the total number of moles ofEO (CH₂CH₂O), and n+z is typically a number from 0 to 15. Specificexamples of Tomamines include Q-14-2 (isodecyloxypropyl dihydroxyethylmethyl ammonium chloride), Q-17-2 (isotridecyloxypropyl dihydroxyethylmethyl ammonium chloride), Q-17-5 (isotridecyloxypropylpoly(5)oxyethylene methyl ammonium chloride), and Q-18-2 (octadecyldihydroxyethyl methyl ammonium chloride).E. Monocarboxylic Acid/Monocarboxylate Component

“Monocarboxylic acid” refers to a hydrocarbon or substituted hydrocarboncontaining only one carboxy functional group (i.e., R¹—C(O)OH).“Monocarboxylate” refers to a salt (i.e., R¹—C(O)OM wherein M is anagriculturally acceptable cation). In one embodiment, the compositioncomprises at least one monocarboxylate salt, which in aqueouscompositions may be present, in whole or in part, in dissociated form asa monocarboxylate anion and the corresponding cation.

Representative monocarboxylic acids and monocarboxylates generallycomprise a hydrocarbon or unsubstituted hydrocarbon selected from, forexample, unsubstituted or substituted, straight or branched chain alkyl(e.g., C₁-C₂₀ alkyl such as methyl, ethyl, n-propyl, isopropyl, etc.);unsubstituted or substituted, straight or branched chain alkenyl (e.g.,C₂-C₂₀ alkyl such as ethenyl, n-propenyl, isopropenyl, etc.);unsubstituted or substituted aryl (e.g., phenyl, hydroxyphenyl, etc.);or unsubstituted or substituted arylalkyl (e.g., benzyl). In oneembodiment, the monocarboxylic acid is selected from the groupconsisting of formic acid, acetic acid, propionic acid, and benzoicacid. In another embodiment, the monocarboxylate salt is selected fromthe group consisting of formate salts, acetate salts, propionate salts,and benzoate salts.

In one embodiment, the herbicidal composition comprises amonocarboxylate salt having the formula R¹—C(O)OM, wherein R¹ isunsubstituted or substituted C₁-C₁₀ alkyl and M is a non-amine,agriculturally acceptable cation. In another embodiment, the herbicidalcomposition comprises a monocarboxylate salt having the formulaR¹—C(O)OM, wherein R¹ is unsubstituted C₁-C₆ alkyl and M is an alkalimetal salt. In another embodiment, the herbicidal composition comprisesa monocarboxylate salt having the formula R¹—C(O)OM, wherein R¹ isunsubstituted C₁-C₃alkyl and M is an alkali metal salt selected fromsodium and potassium. In another embodiment, the monocarboxylate salt ispotassium acetate. In another embodiment, the monocarboxylate salt issodium acetate.

F. Alkali Metal Phosphate

The herbicidal composition concentrates optionally may further includean alkali metal phosphate such as dipotassium phosphate. Dipotassiumphosphate, for example, can provide additional buffering and/orwater-conditioning for aqueous herbicidal compositions of the presentinvention. Dipotassium phosphate is particularly effective as areplacement for ammonium sulfate in herbicidal composition applicationmixtures prepared using hard water.

G. Non-Herbicide Additives

The herbicidal composition concentrates optionally may further includeconventional additives, such as further surfactants, safeners,solubility enhancing agents, thickening agents, flow enhancers,foam-moderating agents, freeze protectants, UV protectants,preservatives, antimicrobials, and/or other additives that are necessaryor desirable to improve the performance, crop safety, or handling of thecomposition.

In any embodiment, the herbicidal composition concentrate can includeless than about 10 ppm of ammonium sulfate. In another embodiment, theherbicidal composition concentrate does not include ammonium sulfate.

In any embodiment, the herbicidal composition concentrate does notinclude an acid other than a monocarboxylic acid.

H. Further Herbicide Components

The herbicidal composition concentrates optionally may include at leastone further herbicide. Representative examples of a further herbicideinclude, but are not limited to hydroxyphenylpyruvate dioxygenase (HPPD)inhibitors, acetyl-CoA carboxylase (ACCase) inhibitors, acetolactatesynthase (ALS) inhibitors, acetohydroxy acid synthase (AHAS) inhibitors,photosystem II (PS II) inhibitors, photosystem I (PS I) inhibitors,protoporphyrinogen oxidase (PPO or Protox) inhibitors, carotenoidbiosynthesis inhibitors, enolpyruvyl shikimate-3-phosphate (EPSP)synthase inhibitor, glutamine synthetase inhibitor, dihydropteroatesynthetase inhibitor, mitosis inhibitors, nucleic acid inhibitors,cellulose inhibitors, oxidative phosphorylation uncouplers,dihydropteroate synthase inhibitors, fatty acid and lipid biosynthesisinhibitors, auxin transport inhibitors, salts and esters thereof,racemic mixtures and resolved isomers thereof, and mixtures thereof;salts and esters thereof; racemic mixtures and resolved isomers thereof;and combinations thereof.

Application mixtures can be prepared by diluting aqueous herbicidalconcentrate compositions as described herein. Additional herbicides canbe “tank mixed” with the application mixtures prepared from the aqueousherbicidal concentrate compositions described herein.

Examples of herbicides within these classes of further herbicides areprovided below. Where an herbicide is referenced generically herein byname, unless otherwise restricted, that herbicide includes allcommercially available forms known in the art such as salts, esters,free acids and free bases, as well as stereoisomers thereof.

Representative examples of HPPD inhibitors include, but are not limitedto aclonifen, amitrole, beflubutamid, benzofenap, clomazone,diflufenican, fluridone, flurochloridone, flurtamone, isoxachlortole,isoxaflutole, mesotrione, norflurazon, picolinafen, pyrazolynate,pyrazoxyfen, sulcotrione, tembotrione, topramezone, tolpyralate,tefuryltrione, salts and esters thereof, and mixtures thereof.

Representative examples of ACCase inhibitors include, but are notlimited to alloxydim, butroxydim, clethodim, cycloxydim, pinoxaden,sethoxydim, tepraloxydim and tralkoxydim, salts and esters thereof, andmixtures thereof. Another group of ACCase inhibitors includechlorazifop, clodinafop, clofop, cyhalofop, diclofop, diclofop-methyl,fenoxaprop, fenthiaprop, fluazifop, haloxyfop, isoxapyrifop, metamifop,propaquizafop, quizalofop and trifop, salts and esters thereof, andmixtures thereof. ACCase inhibitors also include mixtures of one or more“dims” and one or more “fops”, salts and esters thereof.

Representative examples of ALS or AHAS inhibitors include, but are notlimited to amidosulfuron, azimsulfruon, bensulfuron-methyl,bispyribac-sodium, chlorimuron-ethyl, chlorsulfuron, cinosulfuron,cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron-methyl,ethoxysulfuron, flazasulfuron, florazulam, flucarbazone,flucetosulfuron, flumetsulam, flupyrsulfuron-methyl, foramsulfuron,halosulfuron-methyl, imazamethabenz, imazamox, imazapic, imazapyr,imazaquin, imazethapyr, imazosulfuron, iodosulfuron, metsulfuron-methyl,nicosulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone-sodium,prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyrithiobac,rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone,thifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifloxysulfuronand triflusulfuron-methyl, salts and esters thereof, and mixturesthereof.

Representative examples of photosystem I inhibitors include, but are notlimited to diquat and paraquat, salts and esters thereof, and mixturesthereof. Representative examples of photosystem II inhibitors include,but are not limited to ametryn, amicarbazone, atrazine, bentazon,bromacil, bromoxynil, chlorotoluron, cyanazine, desmedipham, desmetryn,dimefuron, diuron, fluometuron, hexazinone, ioxynil, isoproturon,linuron, metamitron, methibenzuron, metoxuron, metribuzin, monolinuron,phenmedipham, prometon, prometryn, propanil, pyrazon, pyridate, siduron,simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazineand trietazine, salts and esters thereof, and mixtures thereof.

Representative examples of PPO inhibitors include, but are not limitedto Diphenylethers (acifluorfen-sodium, bifenox, chlomethoxyfen,chlornitrofen, ethoxyfen-ethyl, fluoroglycofen-ethyl, fomesafen,lactofen, oxyfluorfen), N-phenylphthalimides (cinidon-ethyl, fumiclorac,flumiclorac-pentyl, flumioxazin), oxadiazoles (oxadiargyl, oxadiazon),oxazolidinediones (pentoxazone), phenylpyrazoles (fluazolate,pyraflufen-ethyl), pyrimidindiones (benzfendizone, butafenacil,saflufenacil, ethyl[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate),thiadiazoles (fluthiacet-methyl, thidiazimin), triazinone(trifludimoxazin), triazolinones (azafenidin, carfentrazone-ethyl,sulfentrazone) and others (flufenpyr-ethyl, profluazol, pyraclonil).

Representative examples of carotenoid biosynthesis inhibitors include,but are not limited to aclonifen, amitrole, diflufenican, mesotrione,and sulcotrione.

A representative example of an EPSP inhibitor includes, but is notlimited to N-phosphonomethyl glycine (glyphosate).

A representative example of a glutamine synthetase inhibitor includes,but is not limited to glufosinate.

A representative example of a dihydropteroate synthetase inhibitorincludes, but is not limited to asulam.

Representative examples of mitosis inhibitors include, but are notlimited to acetochlor, alachlor, dithiopyr, S-metolachlor, andthiazopyr.

Representative examples of nucleic acid inhibitors include, but are notlimited to difenzoquat, fosamine, metham, and pelargonic acid.

In any embodiment, the herbicidal composition concentrate furtherincludes a further herbicide selected from the group consisting ofacetochlor, glyphosate, glufosinate, flumioxazin, fomesafen, andagriculturally acceptable salts thereof.

In one embodiment, the herbicidal composition concentrate furtherincludes glyphosate, or an agriculturally acceptable salt thereof.Suitable glyphosate salts include, for example, the ammonium,diammonium, dimethylammonium, monoethanolamine, isopropylamine, andpotassium salts, and combinations thereof. In any embodiment, theglyphosate salts are selected from the group consisting ofmonoethanolamine, isopropylamine, and potassium salts, and combinationsthereof.

In any embodiment, the herbicidal composition concentrate furtherincludes glufosinate, or an agriculturally acceptable salt thereof.

In any embodiment, the herbicidal composition concentrate includesdicamba, or an agriculturally acceptable salt or ester thereof, andglyphosate, or an agriculturally acceptable salt thereof. Additionallyor alternatively, the herbicidal composition concentrate includesdicamba, or an agriculturally acceptable salt thereof; glyphosate, or anagriculturally acceptable salt thereof; and a non-amine, agriculturallyacceptable acetate salt. Commercially available sources of glyphosate,and its agriculturally acceptable salts, include those products soldunder the trade names DURANGO® DMA®, HONCHO PLUS®, ROUNDUP POWERMAX®,ROUNDUP WEATHERMAX®, TRAXION®, and TOUCHDOWN®.

Additionally or alternatively, the herbicidal composition concentrateincludes 2,4-D, or an agriculturally acceptable salt or ester thereof,and glyphosate, or an agriculturally acceptable salt thereof.Additionally or alternatively, the herbicidal composition concentrateincludes 2,4-D, or an agriculturally acceptable salt or ester thereof;glyphosate, or an agriculturally acceptable salt thereof; and anon-amine, agriculturally acceptable acetate salt.

In any embodiment, the herbicidal composition concentrate includesdicamba, or an agriculturally acceptable salt or ester thereof, andglufosinate, or an agriculturally acceptable salt thereof. Additionallyor alternatively, the herbicidal composition concentrate includes 2,4-D,or an agriculturally acceptable salt or ester thereof, and glufosinate,or an agriculturally acceptable salt thereof.

In any embodiment, the herbicidal composition concentrate includes anagriculturally acceptable non-auxin herbicide salt (such as a glyphosatesalt) that is an ionic liquid as described in published applicationUS2013/0109572, i.e., a salt that is a liquid at a temperature at orbelow about 150° C.

I. Component Loading

1. Herbicide Loading:

The herbicidal composition concentrate described herein can be dilutedwith water prior to application. Concentrated herbicidal compositions asdescribed herein typically can include on an acid equivalent basis (a.e.or ae), for example, from about 120 to about 600 g a.e./L, from about300 to about 600 g a.e./L, from about 350 to about 600 g a.e./L, fromabout 400 to about 600 g a.e./L, from about 450 to about 600 g a.e./L,or from about 500 to about 600 g a.e./L total herbicide loading. As usedherein, the term “total herbicide loading” encompasses a herbicideloading when only one herbicide is present in the composition, forexample, one auxin herbicide or one non-auxin herbicide, as well as thetotal when one or more herbicides are present, for example, two auxinherbicides or an auxin herbicide and a non-auxin herbicide. Additionalexamples of representative total herbicide loading include about 120,150, 200, 250, 300, 350, 400, 450, 500, 550, and 600 g a.e./L, andranges thereof (i.e., from about 120 to about 150 g a.e./L, from about150 to about 200 g a.e./L, from about 200 to about 250 g a.e./L, fromabout 250 to about 300 g a.e./L, from about 300 to about 350 g a.e./L,from about 350 to about 400 g a.e./L from about 400 to about 450 ga.e./L, from about 450 to about 500 g a.e./L, from about 500 to about550 g a.e./L, from about 550 to about 600 g a.e./L total herbicideloading).

In any embodiment, the herbicidal composition can be a liquidconcentrate containing, for example, a total amount (acid equivalentweight) of herbicide, by weight of the composition concentrate, ofgreater than or equal to about 5%, greater than or equal to about 10%,greater than or equal to about 15%, greater than or equal to about 20%,greater than or equal to about 30%, greater than or equal to about 40%,greater than or equal to about 50%, greater than or equal to about 60%,or about 70%. Additionally or alternatively, the herbicidal compositionis a liquid concentrate containing, for example, a total amount (acidequivalent weight) of herbicide, by weight of the compositionconcentrate, from about 5% to about 70%, about 5% to about 60%, about 5%to about 50%, about 10% to about 40%, about 10% to about 30%, or aboutor about 10% to about 20%.

In herbicidal compositions concentrates including an auxin herbicide anda non-auxin herbicide, the weight ratio on an acid equivalent basis ofthe auxin herbicide to the non-auxin herbicide is typically no greaterthan about 50:1, for example, about 50:1, 25:1, 10:1, 5:1, 3:1, 2:1,1:1, 1:2, 1:3, 1:5, about 1:10, or ranges thereof such as from about50:1 to about 1:10, from about 50:1 to about 1:5, from about 50:1 toabout 1:1, from about 50:1 to about 3:1, from about 50:1 to about 5:1,from about 50:1 to about 10:1, from about 25:1 to about 1:1, or fromabout 25:1 to about 3:1.

In a particular embodiment, the herbicidal composition concentrate caninclude an auxin herbicide in an amount (acid equivalent weight), byweight of the composition concentrate, of about 5% to about 70%, about5% to about 60%, about 5% to about 50%, about 10% to about 40%, about10% to about 30%, or about or about 10% to about 20%, and non-auxinherbicide in an amount (acid equivalent weight), by weight of thecomposition concentrate, of about 10% to about 70%, about 15% to about60%, about 15% to about 50%, or about 20% to about 40%.

For any given auxin herbicide, one skilled in the art can readilydetermine using routine experimentation a minimum concentration of auxinherbicide and a minimum ratio of auxin herbicide to any additional auxinherbicides and/or non-auxin herbicides contained in the herbicidalcomposition that is desirable for the intended application.

2. Oil Loading:

In any embodiment, the oil or ester thereof as described herein may bepresent in the composition concentrate, by weight of the compositionconcentrate, in a total oil loading of greater than or equal to about1%, greater than or equal to about 1.5%, greater than or equal to about2%, greater than or equal to about 5%, greater than or equal to about8%, greater than or equal to about 10%, greater than or equal to about12%, greater than or equal to about 15%, or about 20%. As used herein,the term “total oil loading” encompasses an oil loading when only oneoil or ester thereof is present in the composition as well as the totalwhen one or more oils and/or esters thereof are present. Additionally oralternatively, the oil or ester thereof may be present in thecomposition concentrate, by weight of the composition concentrate, in atotal oil loading of about 1% to about 20%, about 1% to about 15%, about2% to about 12%, about 2% to about 10%, or about or about 5% to about10%.

Advantageously, the total oil loading in the composition concentratesdescribed herein can provide at least 10 ml of oil sprayed per acre(0.404686 ha), preferably at least 30 ml of oil sprayed per acre(0.404686 ha) when the composition concentrates is sprayed at itsagronomic rate, for example, 560 g acid equivalent per hectare (ha) fordicamba.

3. Polymeric Emulsifying Agent Loading

In any embodiment, the polymeric emulsifying agent as described hereinmay be present in the composition concentrate, by weight of thecomposition concentrate, in a total polymeric emulsifying agent loadingof greater than or equal to about 0.2 wt. %, greater than or equal toabout 0.5 wt. %, greater than or equal to about 0.7 wt. %, greater thanor equal to about 1 wt. %, greater than or equal to about 2 wt. %,greater than or equal to about 3 wt. %, greater than or equal to about 4wt. %, greater than or equal to about 5 wt. %, greater than or equal toabout 6 wt. %, greater than or equal to about 7 wt. %, greater than orequal to about 8 wt. %, greater than or equal to about 9 wt. %, greaterthan or equal to about 10 wt. %, or about 15 wt. %. As used herein, theterm “total polymeric emulsifying agent loading” encompasses a polymericemulsifying agent loading when only one polymeric emulsifying agent ispresent in the composition as well as the total when one or morepolymeric emulsifying agents are present. Additionally or alternatively,the polymeric emulsifying agent may be present in the compositionconcentrate, by weight of the composition concentrate, in a totalemulsifying agent loading of about 0.2 wt. % to about 15% wt. %, about0.2 wt. % to about 15% wt. %, about 0.2 wt. % to about 10 wt. %, about0.5 wt. % to about 10 wt. %, or about 1 wt. % to about 5 wt.

Additionally or alternatively, the polymeric emulsifying agent and theoil or ester thereof as described herein may be present in thecomposition concentrate, by weight of the composition concentrate, in atotal polymeric emulsifying agent and oil loading of greater than orequal to about 0.5 wt. %, greater than or equal to about 0.7 wt. %,greater than or equal to about 1 wt. %, greater than or equal to about 2wt. %, greater than or equal to about 3 wt. %, greater than or equal toabout 4 wt. %, greater than or equal to about 5 wt. %, greater than orequal to about 6 wt. %, greater than or equal to about 7 wt. %, greaterthan or equal to about 8 wt. %, greater than or equal to about 9 wt. %,or greater than or equal to about 10 wt. %. As used herein, the term“total polymeric emulsifying agent and oil loading” encompasses apolymeric emulsifying agent loading when only one polymeric emulsifyingagent and oil and/or ester thereof is present in the composition as wellas the total when one or more polymeric emulsifying agents and one ormore oils and/or esters thereof are present. Additionally oralternatively, the polymeric emulsifying agent and the oil or esterthereof may be present in the composition concentrate, by weight of thecomposition concentrate, in a total emulsifying agent and oil loading ofabout 0.5 wt. % to about 10% wt. %, about 0.5 wt. % to about 8% wt. %,or about 1 wt. % to about 7 wt.

4. Surfactant Loading:

In any embodiment, the surfactant as described herein may be present inthe composition concentrate, by weight of the composition concentrate,in a total surfactant loading of greater than or equal to about 1 wt. %,greater than or equal to about 2 wt. %, greater than or equal to about 3wt. %, greater than or equal to about 4 wt. %, greater than or equal toabout 5 wt. %, greater than or equal to about 6 wt. %, greater than orequal to about 7 wt. %, greater than or equal to about 8 wt. %, greaterthan or equal to about 9 wt. %, greater than or equal to about 10 wt. %,greater than or equal to about 12 wt. %, greater than or equal to about15 wt. %, greater than or equal to about 20 wt. %, greater than or equalto about 25 wt. %, greater than or equal to about 25 wt. %, or about 30wt. %. As used herein, the term “total surfactant loading” encompasses asurfactant loading when only surfactant is present in the composition aswell as the total when one or more surfactants are present. Additionallyor alternatively, the surfactant may be present in the compositionconcentrate, by weight of the composition concentrate, in a surfactantloading of about 1 wt. % to about 30% wt. %, about 1 wt. % to about 25%wt. %, about 2 wt. % to about 25 wt. %, about 3 wt. % to about 25 wt. %,about 4 wt. % to about 25 wt. %, about 5 wt. % to about 25 wt. %, about5 wt. % to about 20 wt. %, about 10 wt. % to about 20 wt. %, about 15wt. % to about 20 wt. %, or about 10 wt. % to about 15 wt. %.

5. Monocarboxylic Acid/Monocarboxylate Loading:

In any embodiment, the herbicidal composition concentrate may include asingle monocarboxylic acid, or monocarboxylate thereof, or a mixture oftwo or more monocarboxylic acids, or monocarboxylates thereof.

In various embodiments, the concentration of volatilized auxin herbicidein the vapor phase surrounding a herbicidal composition comprising anauxin herbicide and a monocarboxylic acid, or monocarboxylate thereof,is less than about 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 5% ofthe concentration of volatilized auxin herbicide in the vapor phasesurrounding the reference composition lacking the monocarboxylate.

The monocarboxylic acid or monocarboxylate loading of the herbicidalcomposition generally can depend upon the auxin herbicide loading of theherbicidal composition, the salt form of the auxin herbicide, and theproperties of any other components of the herbicidal composition, andwill be an amount sufficient to reduce the volatility of the auxinherbicide relative to a reference composition lacking the monocarboxylicacid or monocarboxylate, but otherwise having the same composition. Forexample, the monoethanolamine and diglycolamine salts of dicamba areless volatile than the dimethylamine and isopropylamine salts of dicambaand the loading required for the less volatile salts may be less thanthe loading required for the more volatile salts. In addition, theloading of the monocarboxylic acid, or monocarboxylate thereof, can varywith the specific combination of auxin herbicide, optional non-auxinherbicide, and monocarboxylic acid, or monocarboxylate thereof.

In the herbicidal composition concentrates described herein, the molarratio of the auxin herbicide to the monocarboxylic acid, ormonocarboxylate thereof, is typically no less than about 1:10 and nogreater than about 10:1. Representative molar ratios of auxin herbicideacid equivalent (a.e.) to total monocarboxylic acid, or monocarboxylatethereof, are, for example, from 1:10 to about 10:1, from about 3:10 toabout 10:1, from about 1:5 to about 5:1, and from about 3:1 to about1:3. In any embodiment, the molar ratio of auxin herbicide tomonocarboxylic acid, or monocarboxylate thereof, is about 2:1 to about1:2. In any embodiment, the molar ratio of auxin herbicide tomonocarboxylic acid, or monocarboxylate thereof, is about 1:1.

In any embodiment, the herbicidal composition concentrates can containan amount (acid equivalent weight) of the monocarboxylic acid, ormonocarboxylate thereof, by weight of the concentrate, from about 0.25%to about 35%, about 5% to about 30%, or about 5% to about 20%.

6. Alkali Metal Phosphate/Alkali Metal Carbonate Loading

When the herbicidal composition concentrate includes an alkali metalphosphate, such as dipotassium phosphate, the molar ratio of the alkalimetal phosphate to the monocarboxylic acid, or monocarboxylate thereof,can range, for example, from about 1:5 to about 5:1, from about 3:1 toabout 1:3, or from about 2:1 to about 1:2. In any embodiment, the molarratio of alkali metal phosphate to monocarboxylic acid, ormonocarboxylate thereof, is about 1:1.

When the herbicidal composition concentrate includes an alkali metalcarbonate, such as potassium carbonate, the molar ratio of the alkalimetal carbonate to the monocarboxylic acid, or monocarboxylate thereof,can range, for example, from about 1:5 to about 5:1, from about 3:1 toabout 1:3, or from about 2:1 to about 1:2. In any embodiment, the molarratio of alkali metal carbonate to monocarboxylic acid, ormonocarboxylate thereof, is about 1:1.

J. Methods of Making an Herbicidal Composition Concentrate

Methods of making an herbicidal composition concentrate as describedherein are also provided. The herbicidal composition concentrate formedcan be an emulsion or a micro-emulsion. The method may include admixingat least one herbicide as described herein, for example an auxinherbicide, with an oil or an ester of the oil as described herein and apolymeric emulsifying agent as described herein to form the herbicidalcomposition concentrate. In any embodiment, the oil or the ester of theoil can be admixed with the polymeric emulsifying agent to form a firstmixture, and the at least one herbicide can be admixed with the firstmixture to form the herbicidal composition concentrate. The oil or anester of the oil can be a vegetable oil, an ester of the vegetable oil,or a petroleum-based oil, all as described herein. For example, the oilor the ester of the oil can be selected from the group consistingsoybean oil, an ester of soybean oil, canola oil, an ester of canolaoil, palm oil, an ester of palm oil, rapeseed oil, an ester of rapeseedoil, sunflower seed oil, an ester of sunflower seed oil, corn oil, anester of corn oil, peanut oil, an ester of peanut oil, sesame oil, anester of sesame oil, olive oil, an ester of olive oil, and a combinationthereof.

The polymeric emulsifying agent can be selected from the groupconsisting of glycerol ethoxylate-polyricinoleate (e.g., correspondingto Formula (A) as described herein), glycerolethoxylate-poly-(12-hydroxystearate) (e.g., corresponding to Formula (B)as described herein), polyethylene glycol (PEG)-polyricinoleate (e.g.,corresponding to Formula (C) as described herein),PEG-poly-(12-hydroxystearate) (e.g., corresponding to Formula (D) asdescribed herein), and a combination thereof. The at least one auxinherbicide can be selected from the group consisting of dicamba, anagriculturally acceptable salt of dicamba (e.g.,N,N-[aminopropyl]methylamine, monoethanolamine, dimethylamine,isopropylamine, diglycolamine, a potassium salt, and a sodium salt, anda combination thereof), an agriculturally acceptable ester of dicamba,2,4-D, an agriculturally acceptable salt of 2,4-D, an agriculturallyacceptable ester of 2,4-D, and a combination thereof.

The total herbicide loading of the composition concentrate can be asdescribed herein, for example, an amount (acid equivalent weight) of atleast about 5% to about 50% by weight of the composition concentrate.The total oil loading of the composition concentrate can be as describedherein, for example, an amount of at least about 1.5% by weight of thecomposition concentrate. The total polymeric emulsifying agent loadingof the composition concentrate can be as described herein, for example,an amount of at least about 0.2% by weight of the compositionconcentrate.

In any embodiment, the method may further include admixing the at leastone herbicide with water to form an aqueous solution prior to admixingwith the oil or the ester of the oil and the polymeric emulsifyingagent. Additionally or alternatively, the method may further includeadmixing at least one surfactant as described herein (e.g., a phosphateester, an alkylpolysaccharide, an alkoxylated castor oil, or acombination thereof) with the at least one herbicide, the oil or theester of the oil, and the polymeric emulsifying agent.

Additionally or alternatively, the method may further include admixingat least one monocarboxylic acid (e.g., acetic acid) or amonocarboxylate thereof (e.g., potassium acetate) with the at least oneherbicide, the oil or the ester of the oil, and the polymericemulsifying agent. In any embodiment, the herbicidal compositionconcentrate can contain an amount (acid equivalent weight) of themonocarboxylic acid, or monocarboxylate thereof, by weight of theconcentrate, as described herein, for example, about 5% to about 30%and/or a molar ratio of the at least one monocarboxylic acid or themonocarboxylate thereof to the auxin herbicide as described herein, forexample, from about 1:10 to about 10:1.

Additionally or alternatively, the method may further comprise mixing atleast one further herbicide (e.g., glyphosate, an agriculturallyacceptable salt of glyphosate, glufosinate, an agriculturally acceptablesalt of glufosinate, and a combination thereof) with the at least oneauxin herbicide, with the oil or the ester of the oil and the polymericemulsifying agent. Optionally, an antifoam agent may be added tosuppress formation of foam while mixing. A suitable antifoam agentincludes, but is not limited to a silicone antifoam agent, for example,SAG 1572 available from Momentive. The further herbicide can be presentin the herbicidal composition concentrate in an amount (acid equivalentweight) as described herein, for example, about 15% to about 60% byweight of the composition.

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing from thescope of the invention defined in the appended claims.

EXAMPLES

The following non-limiting examples are provided to further illustratethe present invention. It should be noted that the composition examplesbelow are presented on the basis of the components initially combined toform the reported tank mix or concentrate. The various embodiments ofthe present invention are intended to encompass such initialcompositions as well as any corresponding compositions resulting frominteraction among the components once combined, such as where amonocarboxylic acid salt is formed in situ by combining a monocarboxylicacid with a neutralizing base.

Example 1—Preparation of Glycerol Ethoxylate-4-Ricinoleate

100 g (about 0.1 mol) of glycerol ethoxylate (Mn˜1000) (Product 441864,obtained from Millipore Sigma) was placed in a 3-neck, vacuum-dried500-ml flask equipped with a stir bar and preheated in an 80° C. ovenunder flowing nitrogen. The flask was transferred to a 110° C. oil bathand a septum pierced by a needle, a pressure-equalizing funnel, and aright-angle hose connection adapter, open to the atmosphere (serving asthe exit for nitrogen purge gas) were connected to the necks of theflask. Gentle nitrogen flow was initiated through the needle andstirring was maintained for 10 minutes. 2 g of 25% sodium methoxide inmethanol was added and dropwise addition of 125 g of methyl ricinoleate(4 equivalents) (Product R0029, obtained from TCI Chemicals) wasinitiated. After the addition was complete (1 hour), stirring wascontinued for an additional 30 minutes before adding 1 g of acetic acidand collecting the product. The product was a light yellow, translucentliquid with low viscosity.

The glycerol ethoxylate-4-ricinoleate product was characterized by massspectrometry with matrix-assisted laser desorption ionization(MALDI-MS). Ten microliters each of the glycerolethoxylate-4-ricinoleate product from Example 1 and a matrix solutionwere combined in a microcentrifuge tube and 1 microliter was spottedinto a well of the MALDI-MS sample plate. The matrix solution consistedof 10 g/L α-cyano-4-hydroxycinnamic acid (CHCA), 10 mM NaCl, and 0.1%trifluoroacetic acid in 50% acetonitrile. The samples, along withstandard peptides for mass calibration, were analyzed on an AB SCIEXTOF/TOF 5800 MALDI-MS/MS mass spectrometer. The resultant mass spectrumis shown in FIGS. 1A and 1B. The spectrum of the glycerol ethoxylatestarting material with a NaCl matrix consisted of a series of peaksseparated by 44 mass units—the mass of an ethylene oxide monomer. Thelargest peak, corresponding to the sodium adduct of glycerol with 20 EOunits, was observed at a mass of 995.5 Daltons. As expected, masses werelarger with the glycerol ethoxylate-4-ricinoleate, again with most peaksseparated by 44 mass units. The largest peaks observed corresponded toglycerol ethoxylate with 18, 19, and 20 EO's functionalized with onericinoleate unit, but clusters with two ricinoleate units (20, 21, and22 EO's) and three ricinoleates (22, 23, and 24 EO's) were alsoprominent.

Example 2—Preparation of Glycerol Ethoxylate-7-Ricinoleate

The procedure of Example 1 was repeated for the addition of the firstfour ricinoleate units. A further three equivalents (94 g) were thenadded over 30 minutes followed by another 30 minutes of stirring. Theproduct was a low-viscosity liquid similar to the 4-ricinoleatecondensate.

Example 3—Condensation of PEG 6000 with Six Equivalents of MethylRicinoleate

180 g of PEG, 6000 mol wt. (0.03 mol) (commercially available fromMillipore Sigma) was added to a 500 ml 3-neck, vacuum-dried roundbottomflask equipped with a stir bar and placed in a 90° C. oven to melt thePEG. The flask was transferred to a 110° C. oil bath and a septumpierced by a needle, a pressure-equalizing funnel, and a right-anglehose connection adapter, open to the atmosphere (serving as the exit fornitrogen purge gas) were connected to the necks of the flask. Gentlenitrogen flow was initiated through the needle and stirring wasmaintained for 10 minutes while the PEG came to temperature. 2 g of 25%sodium methoxide in methanol (obtained from Millipore Sigma) was addedat that point.

56 g of methyl ricinoleate (6 equivalents) (Product R0029, obtained fromTCI Chemicals) was added dropwise over 30 minutes and stirring continuedfor a further 70 minutes. The product was a clear liquid with somesuspended white waxy lumps. The product solidified to a white wax afterstanding at room temperature overnight.

Example 4—Condensation of PEG 8000 with Six Equivalents of MethylRicinoleate

The same procedure as Example 3 was followed except the oil bathtemperature was increased to 150° C. due to the higher melting point ofPEG 8000 (commercially available from Millipore Sigma). 160 g of PEG8000 (0.02 mol) was held overnight in the roundbottom flask undernitrogen in a 100° C. oven to melt the PEG. The flask was thentransferred to the oil bath. The procedure in Example 3 was followed,with methyl ricinoleate reduced to 37.5 g (six equivalents) added over70 minutes and 25% sodium methoxide reduced to 1 g due to the increasein PEG molecular weight. Prior to collecting the product, 1 g of aceticacid was added to quench the methoxide catalyst. The product was a clearliquid, which solidified to a hard, white solid upon cooling.

Example 5—MEA Dicamba Formulations with Soybean Oil, PEG-RicinoleateEmulsifying Agents, and High Levels of Potassium Acetate (“Vaporgrip™”)

PEG-6000-6-ricinoleate obtained in Example 3 was dissolved in soybeanoil and a stock solution of the monoethanolamine (MEA) salt of dicambawith an acid equivalent dicamba concentration of 55% was prepared. Theformulation was 26% dicamba on an acid-equivalent basis, which contained1.89 moles of potassium acetate per mole of dicamba for control ofvolatility.

Formulations were prepared with the following composition as shown inTable 1 by combining the components and stirring for about 10 minutes,followed by agitation with an Ika-Turrax T25 high-shear rotor-statormixer operated at a minimum of 15,000 rpm.

TABLE 1 MEA dicamba, 55% ae solution 47.3% Acetic acid 14.1% Potassiumhydroxide, 45% wt/wt 27.8% Crodafos O3A  0.5% PEG-6000-6-ricinoleate insoy oil  5.5% Toximul 8243  1.0% Deionized water  3.8%Variants of the formulation were prepared with 1%, 2%, and 4%PEG-6000-6-ricinoleate in soy oil as well as a comparison formulationwith soy oil alone. These formulations were used for the spray particlesize study in Example 6.

Example 6—Spray Particle Size of Tank Mixtures with Roundup Powermax

Tank mixtures 1, 2, 3, shown in Table 2, were prepared from the dicambaFormulations of Example 5 and Roundup Powermax in tap water to providespray rates of 560/1260 g acid equivalent per hectare dicamba/glyphosateassuming a spray rate of 15 gallons (56.7812 liter) per acre (0.404686ha). A tank mixture of Roundup Xtendimax (a diglycolamine dicambaformulation without a built-in drift retardant) with Powermax was run asa control (Control Tank Mix).

The mixtures were sprayed with two nozzles, the Wilger UR11004 at 50 psiand the Wilger DR11005 at 40 psi in a spray particle size measurementsystem which recirculated the tank mixture. Spray particle size wasmeasured with a Malvern Spraytec laser diffraction spray particle sizeinstrument. The volume percent of the spray consisting of “driftablefines” defined as droplets with diameters below 150 μm is a widelyaccepted measure of the tendency of an agricultural spray to drift.

Table 2 below shows percent fines for these spray mixtures. Inclusion ofsoy oil in the formulations greatly reduces drift and increasing levelsof PEG-6000-6-ricinoleate improve the performance of the soy oil driftretardant with both nozzles.

TABLE 2 Volume % less than 150 μm for 26% ae dicamba formulations withsoy oil containing PEG-6000-6-ricinoleate sprayed at 560 g/ha ae, 15gallons per acre tank mixed with Roundup Powermax I (Tank Mixes 1-3)Polymeric Emulsifying Agent DR11005 UR11004 % in soy oil 40 psi 50 psiTank Mix 1 1% 1.87 ± .15 1.55 ± .01 Tank Mix 2 2% 1.73 ± .04 1.47 ± .03Tank Mix 3 4% 1.68 ± .05 1.42 ± .02 Tank Mix 4 (soy oil only) — 1.78 ±.03 1.55 ± .03 Control Tank Mix- — 3.92 ± .10 2.95 ± .03 Xtendimax(Roundup Xtendimax + PowerMax)

This written description uses examples to disclose the invention,including the best mode, and also to enable any person skilled in theart to practice the invention, including making and using any devices orsystems and performing any incorporated methods. The patentable scope ofthe invention is defined by the claims, and may include other examplesthat occur to those skilled in the art. Such other examples are intendedto be within the scope of the claims if they have structural elementsthat do not differ from the literal language of the claims, or if theyinclude equivalent structural elements with insubstantial differencesfrom the literal languages of the claims.

What is claimed is:
 1. A herbicidal composition concentrate comprising:(a) at least one herbicide present in an amount (acid equivalent weight)of from about 5% by weight to about 70% by weight of the compositionconcentrate, wherein the at least one herbicide comprises an auxinherbicide; (b) an oil or an ester of the oil in an amount of from about1% by weight to about 20% by weight of the composition concentrate; and(c) a polymeric emulsifying agent selected from the group consisting ofglycerol ethoxylate-polyricinoleate, glycerolethoxylate-poly-(12-hydroxystearate), polyethylene glycol(PEG)-polyricinoleate, PEG-poly-(12-hydroxystearate), and a combinationthereof, wherein: the PEG-poly-(12-hydroxystearate) corresponds instructure to Formula D:

wherein j=50 to 250 and s+r=2 to 10, in an amount of from about 0.2% byweight to about 15% by weight of the composition concentrate.
 2. Theherbicidal composition concentrate of claim 1, wherein one or more ofthe following are satisfied: (i) the at least one herbicide is presentin an amount (acid equivalent weight) of about 5% to about 50% by weightof the composition concentrate; (ii) the oil or the ester of the oil ispresent in an amount of from about 1% by weight to about 15% by weightof the composition concentrate; and (iii) the polymeric emulsifyingagent is present in an amount of from about 0.2% by weight to about 10%by weight of the composition concentrate.
 3. The herbicidal compositionconcentrate of claim 1, wherein one or more of the following aresatisfied: (i) the auxin herbicide is selected from the group consistingof dicamba, an agriculturally acceptable salt of dicamba, anagriculturally acceptable ester of dicamba, 2,4-D, an agriculturallyacceptable salt of 2,4-D, an agriculturally acceptable ester of 2,4-D,and a combination thereof; (ii) the oil or the ester of the oil is avegetable oil, an ester of the vegetable oil, or a petroleum-based oil.4. The herbicidal composition concentrate of claim 1, wherein one ofmore of the following are satisfied: (i) the auxin herbicide is anagriculturally acceptable salt of dicamba, wherein the salt is selectedfrom group consisting of N,N-[aminopropyl]methylamine, monoethanolamine,dimethylamine, isopropylamine, diglycolamine, a potassium salt, a sodiumsalt, and a combination thereof; and (ii) the oil or the ester of theoil is selected from the group consisting soybean oil, an ester ofsoybean oil, canola oil, an ester of canola oil, palm oil, an ester ofpalm oil, rapeseed oil, an ester of rapeseed oil, sunflower seed oil, anester of sunflower seed oil, corn oil, an ester of corn oil, peanut oil,an ester of peanut oil, sesame oil, an ester of sesame oil, olive oil,an ester of olive oil, and a combination thereof.
 5. The herbicidalcomposition concentrate of claim 1, wherein: (i) the glycerolethoxylate-polyricinoleate corresponds in structure to Formula A:

wherein i+j+k=10 to 50 and r+s+t=3 to 12; (ii) the glycerolethoxylate-poly-(12-hydroxystearate) corresponds in structure to FormulaB:

wherein i+j+k=10 to 50 and r+s+t=3 to 12; (iii) the polyethylene glycol(PEG)-polyricinoleate corresponds in structure to Formula C:

wherein j=50 to 250 and s+r=2 to 10; and (iv) thePEG-poly-(12-hydroxystearate) corresponds in structure to Formula D:

wherein j=130 to 200 and s+r=3 to
 6. 6. The herbicidal compositionconcentrate of claim 1, further comprising one or more of: (i) asurfactant selected from the group consisting of a phosphate ester, analkylpolysaccharide, an alkoxylated castor oil, and a combinationthereof; and (ii) at least one monocarboxylic acid or a monocarboxylatethereof.
 7. The herbicidal composition concentrate of claim 6, whereinthe at least one monocarboxylic acid or the monocarboxylate thereof ispresent in an amount (acid equivalent weight) of about 5% to about 30%by weight of the composition concentrate; and/or wherein the molar ratioof the at least one monocarboxylic acid or the monocarboxylate thereofto the auxin herbicide is from about 3:10 to about 10:1.
 8. Theherbicidal composition concentrate of claim 6, wherein themonocarboxylic acid is acetic acid or the monocarboxylate is potassiumacetate.
 9. The herbicidal composition concentrate of claim 1, whereinthe at least one herbicide further comprises an herbicide selected fromthe group consisting of glyphosate, an agriculturally acceptable salt ofglyphosate, glufosinate, an agriculturally acceptable salt ofglufosinate, and a combination thereof.
 10. The herbicidal compositionconcentrate of claim 1, wherein the polymeric emulsifying agentcomprises a glycerol ethoxylate-polyricinoleate corresponding instructure to Formula A:

wherein i+j+k=10 to 50 and r+s+t=3 to
 12. 11. The herbicidal compositionconcentrate of claim 1, wherein the polymeric emulsifying agentcomprises a glycerol ethoxylate-poly-(12-hydroxystearate) correspondingin structure to Formula B:

wherein i+j+k=10 to 50 and r+s+t=3 to
 12. 12. The herbicidal compositionconcentrate of claim 1, wherein the polymeric emulsifying agentcomprises a polyethylene glycol (PEG)-polyricinoleate corresponding instructure to Formula C:

wherein j=50 to 250 and s+r=2 to
 10. 13. The herbicidal compositionconcentrate of claim 1, wherein the polymeric emulsifying agentcomprises a PEG-poly-(12-hydroxystearate) corresponding in structure toFormula D:

wherein j=130 to 200 and s+r=3 to
 6. 14. A method of making anherbicidal composition concentrate, the method comprising: admixing atleast one herbicide with an oil or an ester of the oil and a polymericemulsifying agent to form the herbicidal composition concentrate,wherein the at least one herbicide is admixed in an amount (acidequivalent weight) of from about 5% by weight to about 70% by weight ofthe composition concentrate and the at least one herbicide comprises anauxin herbicide, and the oil or ester of the oil is admixed in an amountof from about 1% by weight to about 20% by weight of the compositionconcentrate; wherein the polymeric emulsifying agent is selected fromthe group consisting of glycerol ethoxylate-polyricinoleate, glycerolethoxylate-poly-(12-hydroxystearate), polyethylene glycol(PEG)-polyricinoleate, PEG-poly-(12-hydroxystearate), and a combinationthereof, wherein: the PEG-poly-(12-hydroxystearate) corresponds instructure to Formula D:

wherein j=50 to 250 and s+r=2 to 10, and the polymeric emulsifying agentis admixed in an amount of from about 0.2% by weight to about 15% byweight of the composition concentrate.
 15. The method of claim 14,wherein the oil or the ester of the oil is admixed with the polymericemulsifying agent to form a first mixture and the at least one herbicideis admixed with the first mixture to form the herbicidal compositionconcentrate.
 16. The method of claim 14, wherein the compositionconcentrate comprises one or more of the following: (i) the at least oneherbicide in an amount (acid equivalent weight) of about 5% to about 50%by weight; (ii) the oil or the ester of the oil in an amount of fromabout 1% by weight to about 15% by weight of the compositionconcentrate; and (iii) the polymeric emulsifying agent in an amount offrom about 0.2% by weight to about 10% by weight of the compositionconcentrate.
 17. The method of claim 14, wherein one or more of thefollowing are satisfied: (i) the auxin herbicide is selected from thegroup consisting of dicamba, an agriculturally acceptable salt ofdicamba, an agriculturally acceptable ester of dicamba, 2,4-D, anagriculturally acceptable salt of 2,4-D, an agriculturally acceptableester of 2,4-D, and a combination thereof; and (ii) the oil or the esterof the oil is a vegetable oil, an ester of the vegetable oil, or apetroleum-based oil.
 18. The method of claim 14, wherein one or more ofthe following is satisfied: (i) the auxin herbicide is an agriculturallyacceptable salt of dicamba, wherein the salt is selected from groupconsisting of N,N-[aminopropyl]methylamine, monoethanolamine,dimethylamine, isopropylamine, diglycolamine, a potassium salt, and asodium salt, and a combination thereof; and (ii) the oil or the ester ofthe oil is selected from the group consisting soybean oil, an ester ofsoybean oil, canola oil, an ester of canola oil, palm oil, an ester ofpalm oil, rapeseed oil, an ester of rapeseed oil, sunflower seed oil, anester of sunflower seed oil, corn oil, an ester of corn oil, peanut oil,an ester of peanut oil, sesame oil, an ester of sesame oil, olive oil,an ester of olive oil, and a combination thereof.
 19. The method ofclaim 14, further comprising one or more of: (i) admixing the at leastone herbicide with water to form an aqueous solution prior to admixingwith the oil or the ester of the oil and the polymeric emulsifyingagent; (ii) admixing at least one surfactant with the at least oneherbicide, the oil or the ester of the oil, and the polymericemulsifying agent, wherein the surfactant is selected from the groupconsisting of a phosphate ester, an alkylpolysaccharide, an alkoxylatedcastor oil, and a combination thereof; and (iii) admixing at least onemonocarboxylic acid or a monocarboxylate thereof with the at least oneherbicide, the oil or the ester of the oil, and the polymericemulsifying agent.
 20. The method of claim 14, wherein: (i) the glycerolethoxylate-polyricinoleate corresponds in structure to Formula A:

wherein i+j+k=10 to 50 and r+s+t=3 to 12; (ii) the glycerolethoxylate-poly-(12-hydroxystearate) corresponds in structure to FormulaB:

wherein i+j+k=10 to 50 and r+s+t=3 to 12; (iii) the polyethylene glycol(PEG)-polyricinoleate corresponds in structure to Formula C:

wherein j=50 to 250 and s+r=2 to 10; or (iv) the polyethylene glycolPEG-poly-(12-hydroxystearate) corresponds in structure to Formula D:

wherein j=130 to 200 and s+r=3 to
 6. 21. The method of claim 19, whereinthe composition concentrate comprises the at least one monocarboxylicacid or the monocarboxylate thereof in an amount (acid equivalentweight) of about 5% to about 30% by weight of the compositionconcentrate; and/or wherein the molar ratio of the at least onemonocarboxylic acid or the monocarboxylate thereof to the auxinherbicide is from about 3:10 to about 10:1.
 22. The method of claim 19,wherein the monocarboxylic acid is acetic acid or the monocarboxylate ispotassium acetate.
 23. The method of claim 14, wherein the at least oneherbicide further comprises an herbicide selected from the groupconsisting of glyphosate, an agriculturally acceptable salt ofglyphosate, glufosinate, an agriculturally acceptable salt ofglufosinate, and a combination thereof.